CN114618554B - Iron porphyrin derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material, and preparation method and application thereof - Google Patents
Iron porphyrin derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material, and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 152
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The application discloses an iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material and a preparation method and application thereof, wherein the preparation method of the catalytic material comprises the following steps: mixing ferriporphyrin, metal oxide and carbonate, calcining, mixing with hydrochloric acid solution, ultrasonic treating and standing to obtain the invented catalytic material. According to the preparation method, under the synergistic effect of the metal oxide and the carbonate, the pore structure and the specific surface area of the ferriporphyrin can be obviously improved, and the prepared catalytic material has the advantages of rich pore structure, large specific surface area, multiple active sites, strong stability, excellent catalytic performance and the like.
Description
Technical Field
The application belongs to the field of functional materials, and relates to an iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material, and a preparation method and application thereof.
Background
Since the advent of penicillin in the last century, antibiotics have been widely used in human production and life, the use amount of antibiotics has been increasing with global economic development and population growth, but at the same time, the problems of environmental pollution and ecological risks brought by antibiotics are increasing, because antibiotics cannot be completely absorbed by human or animal bodies after use, a large part of antibiotics can be discharged in the form of raw medicines or metabolites with urine or feces, and the antibiotics migrate and enrich along with water bodies, so that the health of human bodies is seriously affected by food chains, and even adverse effects such as malformation, gene mutation and the like can be generated under the condition of daily accumulation, so that it is urgent to find a method for effectively degrading antibiotic wastewater. Because of the characteristics of large usage amount, strong migration and transformation capability, easy induction of biological generation of resistance genes and the like, the pollution of antibiotics is becoming a hot spot for human research. Common antibiotic treatment techniques, such as membrane filtration, adsorption, oxidation and biological treatment, are limited in practical use due to their high operating costs, complex processes, or the possibility of producing more toxic byproducts. In recent years, the electro-Fenton technology is considered as one of the most developed pollutant treatment technologies due to the factors of green, easy operation and the like. The core of the electro-Fenton technology is the synthesis of the electro-Fenton catalyst, so that the preparation of the electro-Fenton catalyst with high pollutant degradation efficiency, environment friendliness, recoverability and high economic benefit is urgent.
In recent years, metal-intercalated nitrogen-doped carbonaceous materials have been widely used in oxygen reduction reactions due to their excellent electrocatalytic activity and stability. Iron porphyrin is nontoxic in environment, contains abundant iron, nitrogen and carbon elements, and can be used as a precursor of an iron-nitrogen doped carbon catalyst material. However, in the practical application process of the present inventors, it was found that iron element in iron porphyrin derivative particles produced by high-temperature calcination is easily encapsulated by a carbon layer and cannot function. Meanwhile, the present inventors have found that: when a single type of pore-forming agent is used for modifying ferriporphyrin, a modified material with excellent catalytic performance is difficult to obtain, so that the ferriporphyrin derivative material prepared from ferriporphyrin is difficult to effectively degrade organic pollutants, and the possible reasons are that when ferriporphyrin is used as a raw material for high-temperature calcination, the pore structure and the specific surface area of the ferriporphyrin derivative material are difficult to be improved by the single type of pore-forming agent, and the number of active sites exposed on the surface is small, so that the catalytic activity is still poor when the ferriporphyrin derivative material is used as an electro-Fenton catalyst, the effective degradation of the organic pollutants is difficult to realize, and the yield of hydrogen peroxide is difficult to be improved. Therefore, how to obtain the electro-Fenton catalytic material with rich pore structure, large specific surface area, more active sites, strong stability, excellent catalytic performance and environmental friendliness has great significance for improving the removal effect of electro-Fenton catalytic technology on antibiotics and improving the yield of hydrogen peroxide.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide a preparation method of an iron-porphyrin-derived porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material, which has the advantages of rich pore structure, large specific surface area, multiple active sites, strong stability, excellent electro-Fenton catalytic performance and environmental friendliness, and an application of the iron-porphyrin-derived porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material in degrading antibiotics in water or preparing hydrogen peroxide.
In order to solve the technical problems, the application adopts the following technical scheme:
the preparation method of the ferriporphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material comprises the following steps:
s1, mixing ferriporphyrin, metal oxide and carbonate, and calcining at the temperature higher than 600 ℃ to obtain a ferriporphyrin-derived porous ferrinitrogen-doped carbon precursor catalytic material;
s2, mixing the ferriporphyrin-derived porous ferrinitrogen-doped carbon precursor catalytic material prepared in the step S1 with a hydrochloric acid solution, performing ultrasonic treatment, standing, filtering, and drying to obtain the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material.
In the preparation method, further improved, in the step S1, the calcining temperature is 650-800 ℃.
In the preparation method, further improved, in the step S1, the calcining temperature is 680-750 ℃.
In the preparation method, in the step S1, the mass ratio of the ferriporphyrin to the metal oxide to the carbonate is 1-2:1:1; the metal oxide is at least one of magnesium oxide, zinc oxide and copper oxide; the carbonate is at least one of potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate; the calcination is carried out under a protective atmosphere; the protective atmosphere is nitrogen; the temperature rising rate in the calcination process is 5-10 ℃/min; the calcination time is 1-3 h.
In the preparation method, which is further improved, in the step S2, the concentration of the hydrochloric acid solution is 2mol/L; the ultrasonic time is 5-10 min; the standing time is 12-24 hours; the drying is carried out at a temperature of 50-60 ℃.
The application also provides an iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material, which is prepared by the preparation method; the ferriporphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material presents a porous three-dimensional network structure.
As a general technical concept, the application also provides application of the iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material in degrading antibiotics in water or preparing hydrogen peroxide.
The application, when further improved, adopts the ferriporphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material to degrade antibiotics in water, comprises the following steps: mixing the porous iron-nitrogen doped carbon composite electro-Fenton catalytic material derived from iron porphyrin with the antibiotic wastewater to perform electro-Fenton reaction, and completing the degradation of the antibiotic in the water body.
The application is further improved, wherein the electro-Fenton reaction process also comprises the step of adding electrolyte into a reaction system, and the concentration of the electrolyte in the reaction system is 0.05 mol/L-0.1 mol/L; the electrolyte is sodium sulfate.
According to the application, further improved, the electro-Fenton reaction process further comprises the step of introducing air into a reaction system for aeration, wherein the aeration rate of the air is 0.1L/min-1L/min.
In the application, further improved, the three-electrode system constructed in the electro-Fenton reaction process is as follows: the method is characterized by taking a graphite plate electrode as a cathode, a platinum net electrode as an anode and a saturated calomel electrode as a reference electrode.
In the application, the cathode voltage is controlled to be-0.1V to-1.0V in the electro-Fenton reaction process.
In a further development of the above application, the electro-Fenton reaction is carried out under stirring conditions; the stirring rotating speed is 200 r/min-1000 r/min; the time of the electro-Fenton reaction is 30-120 min.
The application is further improved, and the mass ratio of the ferriporphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material to the antibiotics in the antibiotic wastewater is 5-15:1; antibiotics in the antibiotic wastewater comprise ciprofloxacin, tetracycline and terramycin; the initial concentration of the antibiotics in the antibiotic wastewater is 10 mg/L-30 mg/L; the pH value of the antibiotic wastewater is less than or equal to 7.
The application, further improved, when the ferriporphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material is used for preparing hydrogen peroxide, comprises the following steps: mixing the porous iron-nitrogen doped carbon composite electro-Fenton catalytic material derived from iron porphyrin with pure water to perform electro-Fenton reaction to obtain hydrogen peroxide.
The application is further improved, wherein the electro-Fenton reaction process also comprises the step of adding electrolyte into a reaction system, and the concentration of the electrolyte in the reaction system is 0.05 mol/L-0.1 mol/L; the electrolyte is sodium sulfate.
According to the application, further improved, the electro-Fenton reaction process further comprises the step of introducing air into a reaction system for aeration, wherein the aeration rate of the air is 0.1L/min-1L/min.
In the application, further improved, the three-electrode system constructed in the electro-Fenton reaction process is as follows: the method is characterized by taking a graphite plate electrode as a cathode, a platinum net electrode as an anode and a saturated calomel electrode as a reference electrode.
In the application, the cathode voltage is controlled to be-0.1V to-1.0V in the electro-Fenton reaction process.
In a further development of the above application, the electro-Fenton reaction is carried out under stirring conditions; the stirring rotating speed is 200 r/min-1000 r/min; the time of the electro-Fenton reaction is 30-120 min.
According to the application, the initial concentration of the porous iron-nitrogen doped carbon composite electro-Fenton catalytic material derived from iron porphyrin is controlled to be 100mg/L in a reaction system of the electro-Fenton reaction.
Compared with the prior art, the application has the advantages that:
(1) The application provides a preparation method of an ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material, which is characterized in that ferriporphyrin is used as a raw material, metal oxide and carbonate are used as pore-forming agents, and the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material is prepared through calcination treatment. In the application, the metal oxide can react with the carbon-containing precursor substance under the high temperature condition to cause the local corrosion of the carbon layer, so as to form a stable three-dimensional structure; the carbonate can gradually decompose to release carbon dioxide gas along with the rise of temperature, so that micropores of the carbon layer are further enlarged into mesopores and macropores, the porosity and the specific surface area of the mesopores and the macropores are improved, the pore structure and the specific surface area of ferriporphyrin can be remarkably improved through the synergistic effect of the two different types of pore formers, the three-dimensional porous structure prepared by the method not only improves the stability of ferriporphyrin-derived ferrinitrogen-doped carbon catalytic material, but also exposes more active sites (such as FeN x Pyrrole nitrogen, graphite nitrogen and the like), the larger specific surface area increases the contact area of the material and organic pollutant molecules, improves the adsorption capacity of the organic pollutant molecules, and simultaneously promotes the Fenton reaction of iron-containing active sites on the surface of the material and hydrogen peroxide to generate hydroxyl free radicals. The ferriporphyrin derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material prepared by the application has the advantages of rich pore structure and large specific surface area (up to 1677.57 m) 2 Per g), active site number (comprising FeN x FeC, pyrrole nitrogen, graphite nitrogen and the like), strong stability (higher ciprofloxacin degradation efficiency is still shown after multiple cycles), excellent catalytic performance (the ciprofloxacin degradation efficiency reaches 93.82% within 50 min), and the like, can be widely used for degrading organic pollutants (such as antibiotics) in water and preparing hydrogen peroxide, and has high use value and good application prospect.
(2) According to the preparation method of the iron porphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material, iron porphyrin is used as a raw material, and the iron porphyrin contains iron, nitrogen and carbon elements, so that the iron porphyrin can be directly used as a precursor of the iron-nitrogen doped carbon material.
(3) The ferriporphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material prepared by the preparation method provided by the application shows low metal ion leaching rate (concentration of iron ions in solution after 90min reaction)<49.17ug L -1 ) And high reuse rate (76% of ciprofloxacin degradation rate can be achieved after four cycles), and is environment-friendly.
(4) The preparation method of the ferriporphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material has the advantages of simple process steps, mild reaction conditions, less energy consumption, less material consumption, low cost, high preparation efficiency and the like, is suitable for large-scale preparation, and has great significance for industrial popularization.
(5) The application also provides application of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material in degrading antibiotics in water, specifically, the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material is mixed with antibiotic wastewater to perform electro-Fenton reaction, so that the efficient removal of the antibiotics in the water can be realized, and the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material has the advantages of simple process, convenient operation, simple equipment, low cost, high treatment efficiency, good removal effect, cleanness, no pollution and the like, can be widely used for removing the antibiotics in the water, and has very important significance for effectively removing the antibiotics in the water. Taking ciprofloxacin as an example, the porous iron-nitrogen doped carbon composite electro-Fenton catalytic material derived from ferriporphyrin is adopted to perform electro-Fenton reaction for 90min, the removal rate of the ciprofloxacin is up to 99.5%, the efficient removal of the ciprofloxacin is realized, and the practical application requirements can be met.
(6) The application also provides application of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material in preparing hydrogen peroxide, specifically, the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material is mixed with water to perform electro-Fenton reaction, so that the hydrogen peroxide can be prepared, and the hydrogen peroxide has the advantages of simple process, convenient operation, simple equipment, low cost, high preparation efficiency, high yield and the like, wherein the accumulated hydrogen peroxide reaches 182.46mmol within 90min, and has good use value and application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application.
FIG. 1 is an SEM image of an iron porphyrin-derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) prepared in example 1 of the present application.
FIG. 2 is a schematic representation of a ferriporphyrin-derived porous ferrinitrogen prepared in example 1 of the present application TEM image of carbon doped composite electro-Fenton catalytic material (Fe-N-C-700).
FIG. 3 is a Fe2p XPS diagram of the iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) prepared in example 1 of the present application.
FIG. 4 is a Raman diagram of the iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material (Fe-N-C-600, fe-N-C-700, fe-N-C-800) prepared in example 1 of the present application.
FIG. 5 is a graph showing the effect of different catalytic materials on the degradation of ciprofloxacin in a water body in example 2 of the present application.
FIG. 6 is a graph showing the comparison of the degradation rates of ciprofloxacin by different catalytic materials in example 2 of the present application.
FIG. 7 is a graph showing the effect of iron porphyrin-derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) on the degradation of ciprofloxacin in different water bodies.
FIG. 8 is a graph showing the effect of ferriporphyrin-derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) on ciprofloxacin degradation in water bodies with different pH values.
FIG. 9 is a graph showing the comparison of the yields of hydrogen peroxide with respect to the ferriporphyrin-derived porous iron nitrogen-doped carbon composite electro-Fenton catalyst materials (Fe-N-C-600, fe-N-C-700, fe-N-C-800) in example 5 of the present application.
Detailed Description
The application is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the application is not limited thereby.
In the following examples, unless otherwise specified, the materials and equipment used were commercially available, the processes used were conventional, and the equipment used was conventional.
Example 1
The preparation method of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material is characterized in that ferriporphyrin is used as a raw material, magnesium oxide and potassium bicarbonate are used as pore-forming agents, and the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material is prepared through calcination treatment, and comprises the following steps:
s1, respectively weighing 1g of ferriporphyrin, 1g of magnesium oxide and 1g of potassium bicarbonate, fully and uniformly mixing the materials in a quartz vessel, putting the quartz vessel into a quartz boat, and calcining the quartz boat for 2 hours at the temperature of 700 ℃ at the heating rate of 5 ℃ per minute to obtain the ferriporphyrin-derived porous ferrinitrogen-doped carbon precursor catalytic material.
S2, uniformly mixing the porphyrin-derived porous iron nitrogen-doped carbon precursor catalytic material obtained in the step S1 with 100mL of 2mol/L hydrochloric acid solution, and carrying out ultrasonic treatment for 10min to obtain a precursor mixed solution. And standing the precursor mixed solution for 24 hours at room temperature, and then carrying out suction filtration until the solution after suction filtration is neutral. And drying the obtained precursor material for 12 hours at the temperature of 55 ℃ to finally obtain the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material, which is marked as Fe-N-C-700. In the application, other acid solutions except hydrochloric acid solution can not be used for preparing the iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material because of Cl in hydrochloric acid (HCI) solution - Is soluble, can be washed away with the solution and does not destroy the structure of the material itself, while other strong acids, such as sulfuric acid (H) 2 SO 4 ) The catalyst is easy to react with metal ions to generate precipitate which covers the surface of the material, thereby affecting the catalytic effect of the material.
In the embodiment, the adopted iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material (Fe-N-C-700) presents a porous three-dimensional network structure.
Similarly, in this embodiment, different ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic materials (Fe-N-C-600, fe-N-C-800) were prepared at different calcination temperatures, wherein the preparation method of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic materials (Fe-N-C-600, fe-N-C-800) is substantially the same as that of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic materials (Fe-N-C-600), except that: the calcination temperatures of the porous iron-nitrogen doped carbon composite electro-Fenton catalytic materials (Fe-N-C-600 and Fe-N-C-800) derived from the ferriporphyrin are 600 ℃ and 800 ℃ respectively.
In addition, an iron porphyrin derivative electro-Fenton catalyst material (Fe-N-C-700-0) is also prepared in this embodiment, wherein the preparation method of the iron porphyrin derivative electro-Fenton catalyst material (Fe-N-C-700-0) is basically the same as that of the iron porphyrin derivative porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700), and the difference is that: in the method for preparing the ferriporphyrin derivative electro-Fenton catalytic material (Fe-N-C-700-0), no magnesium oxide and potassium bicarbonate are added, i.e. no pore-forming agent is added. The ferriporphyrin derived electro-Fenton catalytic material does not contain a specific pore structure.
In addition, iron porphyrin derived electro-Fenton catalytic materials (Fe-N-C-700-1 and Fe-N-C-700-2) were also prepared in this example, wherein the preparation method of the iron porphyrin derived electro-Fenton catalytic materials (Fe-N-C-700-1 and Fe-N-C-700-2) is basically the same as that of the iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material (Fe-N-C-700), and the only difference is that: in the method for preparing the ferriporphyrin derivative electro-Fenton catalytic materials (Fe-N-C-700-1 and Fe-N-C-700-2), single magnesium oxide and single potassium bicarbonate are respectively used as pore-forming agents.
FIG. 1 is an SEM image of an iron porphyrin-derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) prepared in example 1 of the present application. As can be seen from fig. 1, the iron porphyrin-derived porous iron nitrogen-doped carbon composite electro-Fenton catalytic material prepared by the application has a three-dimensional network structure with multiple pore channels.
FIG. 2 is a TEM image of an iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) prepared in example 1 of the present application. From fig. 2, a number of irregular nitrogen-doped carbon nanospheres and iron-containing spherical particles can be observed. These particles are surrounded by several layers of graphitic carbon with a lattice spacing of 0.354nm, which compact structure is advantageous for reducing leaching of metal ions. Meanwhile, fe-N-C-700 shows clear graphite stripes, which indicates that the graphite has a good graphite structure.
FIG. 3 is a Fe2p XPS diagram of the iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) prepared in example 1 of the present application. As can be seen from FIG. 3, the two peaks at 708.09eV and 721.15eV correspond to Fe2p, respectively 3/2 And Fe2p 1/2 。Fe2p 3/2 The 708.07eV peak of (2) and the 720.96eV peak of Fe2p1/2 are assigned to Fe (II); fe2p 3/2 The 709.93eV peak of (2) and the 723.00eV peak of Fe2p1/2 are assigned to Fe (III).
FIG. 4 is a Raman diagram of the iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material (Fe-N-C-600, fe-N-C-700, fe-N-C-800) prepared in example 1 of the present application. As can be seen from FIG. 4, two distinct peaks 1345cm -1 And 1587cm -1 Corresponds to the D and G bands, respectively, wherein the occurrence of the D band is generally attributed to sp on the graphite plane 3 Defective sites, i.e., heteroatoms and vacancies. The occurrence of the G band is generally due to sp 2 And (3) bonded graphite carbon. Peak intensity ratio of D band and G band (I D /I G ) Can be used to characterize the graphitization degree of the material. In the figure, fe-N-C-700 shows the largest I compared with Fe-N-C-600 and Fe-N-C-800 D /I G This indicates a higher degree of defects and more nitrogen doping, which favors the progress of the electro-Fenton reaction.
Example 2
An application of an ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material in degrading antibiotics in water, in particular to an application of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material as an electro-Fenton catalyst in degrading ciprofloxacin in water, comprising the following steps:
the mass ratio of the catalytic material to ciprofloxacin in the solution is 5:1, taking an iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material (Fe-N-C-600, fe-N-C-700 and Fe-N-C-800) and an iron porphyrin derived electro-Fenton catalytic material (Fe-N-C-700-0, fe-N-C-700-1 and Fe-N-C-700-2) which are prepared in the embodiment 1, respectively adding the materials into a ciprofloxacin solution with the initial concentration of 20mg/L, pH of 3, simultaneously respectively adding sodium sulfate, enabling the concentration of sodium sulfate in a reaction system to be 0.05mol/L, taking a graphite plate electrode as a cathode, taking a platinum mesh electrode as an anode, taking a saturated calomel electrode as a reference electrode, and then introducing air into the reaction solution to perform electro-Fenton catalytic reaction for 90min, wherein the cathode voltage is-0.6V, the aeration amount of air is 0.5L/min, and the rotating speed is 500r/min, and finishing degradation of the ciprofloxacin in a water body. After the reaction is completed, solid-liquid separation is carried out, and the catalytic material in the reaction process is recovered.
In the electro-Fenton catalytic reaction process, the concentration of ciprofloxacin is respectively sampled and measured when the reaction is carried out for 0min, 10min, 20min, 30min, 50min, 70min and 90min, and the degradation efficiency of different catalytic materials on ciprofloxacin in a water body is calculated, and the results are shown in figures 5 and 6.
FIG. 5 is a graph showing the effect of different catalytic materials on the degradation of ciprofloxacin in a water body in example 2 of the present application. As can be seen from FIG. 5, when the porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material derived from iron porphyrin is used for degrading ciprofloxacin in water, ciprofloxacin in water can be effectively removed, wherein the degradation efficiency of the porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material derived from iron porphyrin (Fe-N-C-600, fe-N-C-700 and Fe-N-C-800) on ciprofloxacin after 90min reaction is 18.48%, 99.5% and 77.36%, and the degradation efficiency of the porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material derived from iron porphyrin (Fe-N-C-700-0) is only 13.59%. In addition, the degradation efficiency of the ferriporphyrin derived electro-Fenton catalytic materials (Fe-N-C-700-1 and Fe-N-C-700-2) on ciprofloxacin is about 50%.
FIG. 6 is a graph showing the comparison of the degradation rates of ciprofloxacin by different catalytic materials in example 2 of the present application. As can be seen from FIG. 6, the degradation of ciprofloxacin by the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalyst material (Fe-N-C-600, fe-N-C-700, fe-N-C-800) and the ferriporphyrin-derived electro-Fenton catalyst material (Fe-N-C-700-0) all follow the quasi-first orderThe kinetics, the corresponding order of magnitude of the kinetic constant K values is: fe-N-C-700 (0.0350 h) -1 )>Fe-N-C-800(0.0160h -1 )>Fe-N-C-600(0.0021h -1 )>Fe-N-C-700-0(0.0017h -1 ). Compared with the prior art, the porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material prepared by the application can realize the efficient degradation of ciprofloxacin.
As can be seen from fig. 5 and 6, compared with the ferriporphyrin-derived electro-Fenton catalytic material (Fe-N-C-700-0) without adding the dual pore former (magnesium oxide, potassium bicarbonate), the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material (Fe-N-C-600, fe-N-C-700, fe-N-C-800) prepared after adding the dual pore former (magnesium oxide, potassium bicarbonate) in the application has improved removal efficiency and degradation rate of ciprofloxacin, because the dual pore former can effectively improve the pore density and specific surface area of ferriporphyrin, thereby accelerating the adsorption of pollutants. Meanwhile, under the action of high-temperature calcination, feN in the ferriporphyrin derivative x The active sites of nitrogen-containing species such as pyrrole nitrogen, graphite nitrogen and the like are increased, which is beneficial to promoting the generation of hydrogen peroxide near a cathode in an electro-Fenton reaction system and the generation of hydroxyl free radicals in the Fenton reaction process. Secondly, the porous iron-nitrogen doped carbon composite electro-Fenton catalytic material derived from the ferriporphyrin generated by calcination under different temperature conditions shows different ciprofloxacin degradation efficiency and degradation rate, which indicates that the calcination temperature can obviously influence the modification effect of the dual pore-forming agent on ferriporphyrin. If the temperature is too low, the reaction of the dual pore former with the carbon layer in the ferriporphyrin is local or insufficient; the double pore-forming agent is not effectively reacted with the carbon layer of the ferriporphyrin and is decomposed at high temperature.
Example 3
An application of an ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material in degrading antibiotics in actual water bodies, in particular to an application of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material as an electro-Fenton catalyst in degrading ciprofloxacin in different water bodies, comprising the following steps:
the mass ratio of the catalytic material to ciprofloxacin in the solution is 5:1, taking 4 parts of the iron porphyrin-derived porous iron nitrogen-doped carbon composite electro-Fenton catalytic material (Fe-N-C-700) prepared in the embodiment 1, wherein three parts of the iron porphyrin-derived porous iron nitrogen-doped carbon composite electro-Fenton catalytic material are respectively added into tap water, river water and lake water with the initial concentration of 20mg/L, pH of ciprofloxacin, sodium sulfate is respectively added at the same time, so that the concentration of sodium sulfate in a reaction system is 0.05mol/L, a graphite plate electrode is used as a cathode, a platinum mesh electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, a three-electrode system is constructed, and then air is introduced into a reaction solution for electro-Fenton catalytic reaction for 90min, wherein the cathode voltage is-0.6V, the aeration amount of the air is 0.5L/min, and the rotating speed is 500r/min, so that the degradation of ciprofloxacin in a water body is completed. After the reaction is completed, solid-liquid separation is carried out, and the catalytic material in the reaction process is recovered.
In the electro-Fenton catalytic reaction process, the concentration of ciprofloxacin is respectively sampled and measured when the reaction is carried out for 0min, 10min, 20min, 30min, 50min, 70min and 90min, the degradation efficiency of the ferriporphyrin-derived porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material on ciprofloxacin in different types of water bodies is obtained through calculation, and the result is shown in figure 7.
FIG. 7 is a graph showing the effect of iron porphyrin-derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) on the degradation of ciprofloxacin in different water bodies. As can be seen from FIG. 7, the degradation efficiency of the iron porphyrin-derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material on ciprofloxacin in tap water, river water and lake water is 89.27%, 42.55% and 96.16%, respectively, which indicates that the iron porphyrin-derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material has higher degradation performance on ciprofloxacin in different water environments, and the degradation performance on ciprofloxacin in lake water is slightly lower than that of tap water and river water, which may be caused by that a large amount of organic impurities existing in lake water adhere to the catalytic material, so that part of the catalytic material cannot be effectively contacted with a solution. In general, the ferriporphyrin-derived porous ferrinitrogen-doped carbon electro-Fenton catalytic material can be widely used for treating ciprofloxacin in different water environments, and has good practical application prospects in the electro-Fenton field.
Example 4
An application of an ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material in degrading antibiotics in water, in particular to an application of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material as an electro-Fenton catalyst in degrading ciprofloxacin in water with different pH values, comprising the following steps:
the mass ratio of the catalytic material to ciprofloxacin in the solution is 5:1, taking 4 parts of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material (Fe-N-C-700) prepared in the embodiment 1, wherein three parts of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material are respectively added into ciprofloxacin solutions with the pH value of 3, 5 and natural conditions (pH value of approximately 6) and 7, the initial concentration of ciprofloxacin in the solutions is 20mg/L, sodium sulfate is respectively added at the same time, the concentration of sodium sulfate in a reaction system is 0.05mol/L, a graphite plate electrode is used as a cathode, a platinum mesh electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, and then air is introduced into the reaction solution to perform electro-Fenton catalytic reaction for 90min, wherein in the electro-Fenton catalytic reaction process, the cathode voltage is-0.6V, the aeration amount of air is 0.5L/min, and the rotation speed is 500r/min, so that the degradation of the ciprofloxacin in a water body is completed. After the reaction is completed, solid-liquid separation is carried out, and the catalytic material in the reaction process is recovered.
In the electro-Fenton catalytic reaction process, the concentration of ciprofloxacin is respectively sampled and measured when the reaction is carried out for 0min, 10min, 20min, 30min, 50min, 70min and 90min, the degradation efficiency of the ferriporphyrin-derived porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material on ciprofloxacin in water bodies with different pH values is calculated, and the result is shown in figure 8.
FIG. 8 is a graph showing the effect of ferriporphyrin-derived porous iron nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) on ciprofloxacin degradation in water bodies with different pH values. As can be seen from FIG. 8, the porous iron-nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) derived from iron porphyrin has degradation efficiencies of 96.08%, 77.43%, 73.77% and 66.3% on ciprofloxacin in ciprofloxacin solutions with pH values of 3, 5 and natural conditions (pH value of about 6) and 7, respectively, which indicates that an acidic reaction system with lower pH value is more beneficial to the performance of electro-Fenton reaction because hydrogen ions rich in the solution can promote two-electron reduction reaction to generate hydrogen peroxide, and further increase the generation amount of hydroxyl free radicals.
Example 5
An application of a ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material in preparing hydrogen peroxide, in particular to a preparation method of hydrogen peroxide by taking a ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material as an electro-Fenton catalyst, comprising the following steps:
according to the initial concentration of the catalyst being 100mg/L, the iron porphyrin derived porous iron nitrogen doped carbon composite electro-Fenton catalytic material (Fe-N-C-600, fe-N-C-700 and Fe-N-C-800) prepared in the example 1 is respectively added into pure water, sodium sulfate is respectively added at the same time, so that the concentration of sodium sulfate in a reaction system is 0.05mol/L, a graphite plate electrode is used as a cathode, a platinum mesh electrode is used as an anode, a saturated calomel electrode is used as a reference electrode, a three-electrode system is constructed, then air is introduced into the reaction solution to perform electro-Fenton catalytic reaction for 90min, wherein in the electro-Fenton catalytic reaction process, the cathode voltage is-0.6V, the aeration rate of the air is 0.5L/min, and the rotating speed of the air is 500r/min.
During the electro-Fenton catalytic reaction, the concentration of hydrogen peroxide is respectively sampled and measured when the reaction is carried out for 0min, 10min, 20min, 30min, 50min, 70min and 90min, and the influence of different catalytic materials on the hydrogen peroxide yield is calculated, so that the result is shown in figure 9.
FIG. 9 is a graph showing the comparison of the yields of hydrogen peroxide with respect to the ferriporphyrin-derived porous iron nitrogen-doped carbon composite electro-Fenton catalyst materials (Fe-N-C-600, fe-N-C-700, fe-N-C-800) in example 5 of the present application. As can be seen from FIG. 9, the porous iron-nitrogen doped carbon composite electro-Fenton catalyst material (Fe-N-C-700) derived from the iron porphyrin has the maximum hydrogen peroxide generation amount, and achieves accumulation of 182.46mmol within 90min, and the generation amounts of 96.67mmol, 151.85mmol and 101.85mmol of the Fe-N-C-600 electro-Fenton system, the Fe-N-C-800 electro-Fenton system and the system without any catalyst are respectively. The application relates to a porous iron-nitrogen doped carbon composite electro-Fenne derived from ferriporphyrinFens contained in the photocatalytic material x Active sites of nitrogen-containing species such as pyrrole nitrogen and graphite nitrogen can effectively promote electron transfer in a reaction system, so that hydrogen peroxide in the system is promoted to be generated. It can be seen that the calcination temperature affects the modification effect of the dual pore former on various species in the ferriporphyrin, thereby affecting the formation of hydrogen peroxide.
In summary, in the preparation method of the application, the pore structure and specific surface area of ferriporphyrin can be obviously improved through the synergistic effect of the two different types of pore formers (metal oxide and carbonate), and the three-dimensional porous structure prepared by the method not only improves the stability of ferriporphyrin-derived ferrinitrogen-doped carbon catalytic material, but also exposes more active sites (such as FeN x Pyrrole nitrogen, graphite nitrogen and the like), the larger specific surface area increases the contact area of the material and organic pollutant molecules, thereby preparing the material with rich pore structure and large specific surface area (up to 1677.57m 2 Per g), active site number (comprising FeN x The preparation method has the advantages of being strong in stability (high in ciprofloxacin degradation efficiency after repeated circulation), excellent in catalytic performance (93.82% of ciprofloxacin degradation efficiency is achieved in 50 min), and the like, and when the porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material is used as an electro-Fenton catalyst for degrading organic pollutants (such as antibiotics) in water or preparing hydrogen peroxide, the adsorption capacity of molecules of the organic pollutants is improved, meanwhile, fenton reaction of iron-containing active sites on the surface of the material and the hydrogen peroxide to generate hydroxyl radicals is promoted, so that not only can effective degradation of the organic pollutants (such as antibiotics) be achieved, but also the yield of the hydrogen peroxide can be remarkably improved, wherein the electro-Fenton reaction is carried out for 90min by taking ciprofloxacin as an example, the removal rate of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material is up to 99.5%, the efficient removal of the ciprofloxacin is realized, meanwhile, the requirements of the effective removal of the ciprofloxacin can be met, and the hydrogen peroxide can be well accumulated in the application range of 62 mmol and 3890 mmol can be achieved.
The above examples are only preferred embodiments of the present application, and the scope of the present application is not limited to the above examples. All technical schemes belonging to the concept of the application belong to the protection scope of the application. It should be noted that modifications and adaptations to the present application may occur to one skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (3)
1. The application of the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material in degrading antibiotics in water or preparing hydrogen peroxide is characterized in that the ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material is adopted to degrade the antibiotics in the water, and the application comprises the following steps: mixing the ferriporphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material with antibiotic wastewater to perform electro-Fenton reaction, so as to finish the degradation of the antibiotics in the water body; the mass ratio of the porous iron-nitrogen doped carbon composite electro-Fenton catalytic material derived from the ferriporphyrin to the antibiotics in the antibiotic wastewater is 5-15:1; the antibiotic in the antibiotic wastewater is ciprofloxacin; the initial concentration of the antibiotics in the antibiotic wastewater is 10 mg/L-30 mg/L; the pH value of the antibiotic wastewater is 3;
when the ferriporphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material is used for preparing hydrogen peroxide, the method comprises the following steps: mixing a porous iron-nitrogen-doped carbon composite electro-Fenton catalytic material derived from ferriporphyrin with pure water to perform electro-Fenton reaction to obtain hydrogen peroxide; the initial concentration of the porous iron-nitrogen doped carbon composite electro-Fenton catalytic material derived from iron porphyrin is controlled to be 100mg/L in a reaction system of the electro-Fenton reaction;
the preparation method of the ferriporphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material comprises the following steps:
s1, mixing ferriporphyrin, metal oxide and carbonate, and calcining at 680-700 ℃ to obtain a ferriporphyrin-derived porous ferrinitrogen-doped carbon precursor catalytic material; the metal oxide is at least one of magnesium oxide, zinc oxide and copper oxide;
s2, mixing the ferriporphyrin-derived porous ferrinitrogen-doped carbon precursor catalytic material prepared in the step S1 with a hydrochloric acid solution, performing ultrasonic treatment, standing, filtering and drying to obtain a ferriporphyrin-derived porous ferrinitrogen-doped carbon composite electro-Fenton catalytic material;
the ferriporphyrin-derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material presents a porous three-dimensional network structure.
2. The use according to claim 1, wherein the electro-Fenton reaction process further comprises adding electrolyte to the reaction system, wherein the concentration of the electrolyte in the reaction system is 0.05mol/L to 0.1mol/L; the electrolyte is sodium sulfate;
the electro-Fenton reaction process also comprises the steps of introducing air into a reaction system for aeration, wherein the aeration rate of the air is 0.1L/min-1L/min;
the three-electrode system constructed in the electro-Fenton reaction process is as follows: the method comprises the steps of taking a graphite plate electrode as a cathode, a platinum net electrode as an anode and a saturated calomel electrode as a reference electrode;
the cathode voltage is controlled to be-0.1V to-1.0V in the electro-Fenton reaction process;
the electro-Fenton reaction is carried out under the stirring condition; the stirring rotating speed is 200 r/min-1000 r/min; the time of the electro-Fenton reaction is 30-120 min.
3. The use according to claim 1, wherein in step S1, the mass ratio of iron porphyrin, metal oxide and carbonate is 1-2:1:1; the carbonate is at least one of potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate; the calcination is carried out under a protective atmosphere; the protective atmosphere is nitrogen; the temperature rising rate in the calcination process is 5-10 ℃/min; the calcination time is 1-3 h;
in the step S2, the concentration of the hydrochloric acid solution is 2mol/L; the ultrasonic time is 5-10 min; the standing time is 12-24 hours; the drying is carried out at a temperature of 50-60 ℃.
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